Morphology of cold-drawn high-density

polyethylene fibres
W. G. Harland, M. M. Khadr and R. H. Peters
Department of Polymer and Fibre Science, University of Manchester Institute of Science
and Technology, Manchester M60 1QD, UK
(Received 11 June 1973; revised 22 August 1973)

Drawn fibres of high-density polyethylene, and their crystalline residues obtained by

nitric acid digestion of the amorphous phase, exhibit single- or double-peaked melting
endotherms depending on the degree of crystallinity of the fibre, the draw ratio and, in
the case of some of the crystalline residues, whether or not they have been melted once
or twice. The melting behaviour of the drawn fibres and their crystalline residues has
been accounted for in terms of the rupture of a fraction of the original lamellar structure
and the growth of a new crystalline structure.

INTRODUCTION
There is a considerable amount of evidence to show
that the process of cold drawing high-density poly-
ethylene (HDPE) involves rupture of the original
lamellar structure and the formation of a new crystalline
microfibrillar structure 1-5. At some intermediate stage
of drawing at least two different crystalline entities must
co-exist and they would be expected to have different
melting points; nevertheless drawn HDPE products
with two or more melting points have not been reported.
However, Meinel et al. z,6 have observed that the
crystalline residues obtained from drawn HDPE film
by removing the amorphous fraction with nitric acid
yield endotherms with twin peaks when melted a second
time; furthermore, the position on the temperature
axis of one of the twin peaks was observed to change
markedly as drawing proceeded. Twin melting peaks
were not observed with undrawn and drawn parent
films, with crystalline residues from undrawn film, or
with crystalline residues from drawn film after a first
melting.
Meinel and Peterlin attributed the low-temperature
peak ( L T P ) to the presence of lamellae which had had
their folds cut by the nitric acid treatment, and the
high temperature peak ( H T P ) to the melting of a
crystalline entity formed from tie molecules which had
survived the nitric acid treatment. They argued that
initially these two components of differing low molecular
weight would constitute a molecular mixture and as
such exhibit a single melting point, but would separate
by a process of fractional crystallization during solidifica-
tion after melting, and when remelted would exhibit
separate melting points.
The validity of these arguments is dependent on tie
molecules surviving the nitric acid treatment, for which
the evidence is slender. Meinel and Peterlin 6 considered
that to a first approximation the elastic modulus of the
acid-treated films should be proportional to the number
of tie molecules. They claimed that for as long as the
modulus could be measured, namely for up to 8h
treatment with acid, the value was practically unchanged.
After further acid treatment the specimens were too
brittle to make measurements with. This evidence is not
satisfactory in that their data show a decrease in modulus
of 13~o and, more significantly still, show that after
8 h treatment the weight loss was only 5 or 6 % whereas
the samples whose melting endotherms were under
consideration were derived from film that had received
50 h acid treatment and suffered a weight loss equal to
its amorphous content (about 25 ~).
The investigations of Meinel et al. 3, 6 were confined to
two moulded samples of HDPE film, one of which had
been slowly cooled and the other quench cooled to
yield isotropic products of 75 and 68 % crystallinity
respectively. The absence of twin melting points in the
endotherms of drawn film and uncertainty as to the
identity of the two crystalline fractions giving rise to
twin peaks in the melting endotherms of the crystalline
residues, prompted the authors of this paper to conduct
a similar investigation with samples of HDPE in a lower
but overlapping range of initial degree of crystallinity,
and with samples also differing in initial degree of
orientation. Since these two parameters are difficult
to vary with films the necessary samples were obtained
by extrusion as fibres. It has been found that a fibre
containing about 6 0 ~ crystalline material (hereafter
designated 60-fibre) gives, after drawing, a twin-peaked
melting endotherm, while fibres of 67.5 and 70 % crystal-
linity (67-5-fibre and 70-fibre) yield only single peaks.
The crystalline residues derived from the 60-fibre (60-
residues) yield twin peaks when melted or remelted,
whereas the 67.5 and 70 residues have endotherms with
twin peaks only when remelted. At very high draw
ratios all fibres and crystalline residues have a single
melting point. In addition to studying melting behaviour,
the degree of crystallinity of the fibres and the molecular
weight of the crystalline residues have been measured at
various draw ratios.
The discovery that HDPE of lower degree of crystal-
linity than that used by Meinel et al. a, 6 yields cold-

POLYMER, 1974, Vol 15, February 81

Morphology of cold-drawn HDPE fibres: W. G. Harland et aL
drawn products which have melting endotherms with Table 1 Crystalline content ( ~ ) from AH and nitric acid digestion
twin peaks, and that the crystalline residues derived
from these products exhibit endotherms with cor- 60-fibre 60-fibre
70-fibre (An=0.0016) (An=0.012)
responding twin peaks during melting and remelting,
has simplified the identification of the crystalline fractions Draw ratio AH HNOa AH HNOa AH HNOa
responsible for the twin-peak phenomenon. Arguments
are put forward to show that in the initial stages of Undrawn 71 71 60 62 60 61
drawing they are the torn-off blocks of folded chains 10 74 75 77 76 74 74
15 75 75 79 78 75 75
and the original lamellae; the former constituting the 20 76 76 80 80 76 75
LTP and the latter the HTP. As drawing proceeds both 25 77 76 81 81 m
components undergo modification and the changes in
melting characteristics of both fibres and residues are
consistent with partial destruction of the original washed in water until free from acid, extracted with
lamellae and formation of a new crystalline structure. hot acetone for 4h, and dried in vacuo at 60°C to constant
While the conclusions as to the identity and origins weight. The main requirement of the nitric acid treatment
of the crystalline fractions differ from those of Meinel is that it should be adequate to remove all the amorphous
and Peterlin6 they are in qualitative agreement with the phase from a variety of fibres which differ in crystaUinity
accepted mechanism of deformation and with models and orientation. Table 1 compares degree of crystaUinity
proposed for the crystalline fibrillar structure of oriented calculated from heat of fusion with percentage weight
polyethylenO-5. of residual material. The two sets of figures are very
Notwithstanding the above conclusions, consideration similar and, since those derived from residual weight
has also been given to the possibility that the presence are inflated slightly by the presence of terminal carboxyl
of twin melting points in endotherms obtained when groups, it follows that the duration of acid treatment
crystalline residues are melted a second time is connected was more than adequate.
with the presence of buried chain folds in lamellae. It
is possible that fractional crystallization would occur Molecular weight of crystalline residues
during solidification after a first melting and the endo- Intrinsic viscosities were determined from decalin
therm of remelting would have multiple peaks corres- solutions at 120°C and viscosity-average molecular
ponding to multiple traverses of the lamellae. However, weights were calculated from the expressionS:
twin melting peaks are not observed in undrawn HDPE
or their corresponding crystalline residues, although [~7]=2"76 x 10-4~v) 0.7s
Ward and Williams7 have obtained gel permeation
Values at different draw ratios are given in Table 2.
chromatograms with multiple peaks from such residues.
Owing to the presence of buried and uncut chain folds
When the residues of drawn HDPE are investigated
the molecular weights give only a rough indication of
multiple peaks in melting endotherms are formed but
fold length.
not in gel permeation chromatograms. The two pheno-
mena appear to be mutually exclusive.
Melting endotherms
EXPERIMENTAL The endotherms were determined with a Perkin-Elmer
differential calorimeter Model DSC-1. Samples of
Polymer known weight (3--4mg), were heated in dry nitrogen
Commercial HDPE (Code No. 65.045) was supplied (18 ml/min) at a rate of 8 °C/rain. In the case of crystalline
by Shell Plastics Laboratory, Carrington. It had a residues heating was continued to 10°C above the
viscosity-average molecular weight of 6.0 x 104 and a melting point and the sample was cooled in the instru-
melt flow index of 4-5g/10min at 190°C. ment at 8°C/rain. The thermogram for remelting was
obtained from the newly crystallized sample with the
Fibres same rate of heating as before. Percentage crystallinities
Fibres were extruded at 200°C from a rod-type were derived from heats of fusion and a value for
spinning unit. The output rate was kept constant, but crystalline polyethylene of 66 cal/g.
the wind-up velocity and the distance below the spinneret
at which the fibres were quench-cooled in water was
RESULTS AND DISCUSSION
varied. Variation of these two parameters provided
fibres of different degree of crystaUinity and different Fibres
birefringence as shown in Table 2. From a wide variety of experimental methods an
impressive amount of evidence has been accumulated
Drawing procedure to show that cold drawing HDPE involves rupture of
Filaments (2cm lengths) were drawn at 23°C and the original lamellar structure and the formation of
0.5 cm/min on an Instron machine. Samples were drawn crystalline microfibrils from small blocks of folded
to their natural draw ratio and to draw ratios of 10, chains 1-5. The derivation by Meinel and Petedin z
15 and 20. The natural draw ratio was calculated as of a differential work density curve from a true stress-
the ratio of the cross-sectional area of fibre in the relaxed strain curve is particularly informative since it deafly
state before and after drawing. demonstrates the existence of two more or less simul-
taneous deformation mechanisms--destruction of the
Oxidation with nitric acid original lamellar structure and deformation of the new
Samples of drawn and undrawn fibres were treated structure. It was proposed that the second process
with 95 ~o nitric acid at 80°C for 50 h. The residues were occurs by longitudinal slip of microfibrils which a r e

82 POLYMER, 1974, V o l 15, F e b r u a r y

 Morphology of cold-drawn HDPE fibres: W. G. Harland et aL
Table 2 Properties of fibres and crystalline residues

70-fibre: (280)a (9.2)b (19.5)c (0.60)d 67.5-fibre: (260)a (6.8)b

Draw Crystallinitye MW of Crystallinity MW of
ratio (~/o) Anf residues (~/o) An residues
Undrawn 70.8 0.0015 1360 67-5 0.0018 1160
10 74.0 0.016 1500 75.2 0.029 1480
15 75.2 0- 022 1540 76- 8 0.039 1560
20 75.9 0.095 1610 77.9 0.040 1670
Rupture 77.9 . . . . .
60-fibre(low An): 60-fibre(high An):
(220)a (5" 1)b (22-1)c (0.24)d (45)a (2.6)b (21-2)c (0.80)d

Undrawn 60.4 0.0016 1000 60.0 0-012 1100

10 77.0 0.035 1640 74.0 0.032 1540
15 79.1 0.050 1740 74.8 0.044 1670
20 80.2 0.051 1750 76.0 0.046 1720
Rupture 81.3 -- -- 80.2 --
a Filament denier (g/9000m)
b Natural draw ratio
c Ultimate strength based on final denier (g/denier)
d Ratio of nominal tenacities at yield and rupture
e Derived from heats of fusion
f Measured with a polarizing microscope and a calibrated quartz-wedge compensator

connected together by relatively few fie molecules. To a b

this interpretation of the drawing process must be 129oc 130'5°C
added changes which occur in total crystalline content
and in fold length (Table 2). Nevertheless, it is not at
variance with the established concepts to suggest that
during drawing, segmental and molecular mobility are
so enhanced that increases in degree of crystallinity

~
and fold length may readily occur. The data in Table 2
suggest that the increase in crystallinity is largely 9.5oc 131oc
accounted for by the increase in fold length. It is antici-
pated that increases in fold length may occur both in
the remainder of the original lamellae and in the smaller
blocks of folded chains. It should, however, be easier
for fold length increases to occur in the latter since 131"5°C 131.5oC
the co-operative movement of a smaller number of
folds will be required.
The melting behaviour of the fibres and their crystal-

~
line residues must be related to morphological changes
accompanying drawing. The melting endotherms of 2 5°C
60-fibres at their natural draw ratios (Figure 1) clearly 132oc
show that a new crystalline species of lower melting
point is being created. In order to explain the lower
melting point it must be assumed that the size of the
crystal units are less than in the original lamellae such 133°C
that the surface free energy contribution to melting is
increased, and/or the fold length has decreased. Esti-
mates of crystal dimensions from the line broadening of
wide-angle X-ray scattering, and calculations of crystal-
thickness from the long period obtained by small-angle
X-ray scattering show that both changes may occur
during drawing 9. The fraction of lower melting point J (2C ~'
is, therefore, identified with torn-off blocks from the
Figure 1 Melting end0therms of 60-fibres at
original lamellae, and the fraction of higher melting draw ratios shown in parentheses. An un-
point with the original lamellae. drawn state: (a) 0.0016; (b) 0.012. Peak tem-
As drawing proceeds both peak temperatures increase peratures indicated
but that of the LTP increases the more rapidly (Figure 1).
These changes are a reversal of those occurring in the Meinel and Peterlin 1 are of the opinion that with HDPE
initial stages of drawing and may be attributed to a film destruction is complete at a draw ratio of about
differential rate of fold growth and aggregation of small 10, but the fact that the height of the HTP is maintained
crystals into larger units (fibrils) with a lower surface up to draw ratios of at least 15 suggests otherwise for
free energy. Owing to lack of resolution of the two fibres. This view is supported by evidence derived from
peaks it is not clear whether the whole or only a part the endotherms of the crystalline residues which is
of the original lamellar structure is destroyed by drawing. discussed later.

P O L Y M E R , 1974, V o l 15, February 83

Morphology of cold-drawn HDPE fibres: W. G. Harland et aL

a b the widths of the peaks at half height increase from

131oc 130.5oc 1.5 to 2"1°C and 1.5 to 3.7°C for 70- and 67.5-fibres
respectively. Thus there is no reason to suppose that
the morphology and melting behaviour of the drawn
versions of the fibres of relatively high crystallinity are
in any way anomalous.
At high extents of drawing (Figures 1 and 2) only
a single melting peak is observed for all fibres regardless
of their original degree of crystallinity and orientation,
which is consistent with the formation of a homogeneous
fibrillar structure. It is interesting but not surprising
that at ultimate elongation the fibres have the same
melting point (135 ° + 0.5°C), a similar degree of crystal-
linity, and a similar tensile strength (Table 2). It is
possible that if a much lower rate of drawing had been
used differences would be even less.

Crystalline residues
32°C 132"5°C Having established the identity of the two crystalline
fractions responsible for the twin melting peaks of fibres,
it is necessary to consider their relation to the melting
endotherms of residues. By comparing Figures 1, 2
and 3 it may be seen that in terms of the existence of
single or twin melting peaks at equal draw ratios, and
after the first melting of the residues, the residues and
fibres are strictly comparable. However, where twin
peaks exist in fibres and residues there is a noticeable
difference in the degree of resolution of the two peaks.

a b C
(201 12OI 124oc 124.5 o C 124.5oc
Figure 2 Melting endotherms of (a) 70-fibres
and (b) 67.5-fibres at drawn ratios shown in
parentheses. An undrawn state: (a) 0.0015;
/~1
124"5°C 125oc 25:5°C

(b) 0.0018. Peak temperatures indicated (11)[i

Drawn fibres of 67"5 and 70% crystallinity do not
appear to have two melting points (Figure 2). Since
. <
there is no reason to suspect that a different deformation ~ 1260c AI25oc 125oc
mechanism applies, the possibility that twin melting A
points exist at extents of deformation less than the |I l | 127"5°C• ll.q127°C
natural draw ratio must be examined. There is no (lol H ~28oc I I ,~ III'
I I ,'l IIi I I I/I
reason to expect equivalent structural changes to occur ll/; 122soc/ V~ ,,~o / A !
at equal extents of deformation in materials with different
natural draw ratios. This situation arises first because
drawing takes place in two stages--drawing to the ~ 127°C ^127°C 126.5oc
natural draw ratio at a neck followed by uniform
extension of the material which has already been drawn 28°C I//t 128'5°C jq~h128oc
to its natural draw ratio, and secondly, because the (!.s) .IY, 111 li'i
rate of deformation, and hence the intensity of deforma-
tion, is enormously greater when drawing is proceeding
..o#'i
,24o I 2,,o ,i 1
at a neck. Thus at equal draw ratios different extents _-- J ~ i- L.,,','~,2~k'<.
of morphological change are to be expected in 67.5-, 129oc ~128oc
70-, and 60-fibres of low and high orientation, which
have draw ratios of 9-2, 6.8, 5.1 and 2-6 respectively. I[,e
In particular the significant morphological changes
which give rise to twin melting endotherms appear at / II
I
!1= I
lower extents of deformation the higher the natural
draw ratio. Furthermore, close inspection of Figure 2 . . . . , < ...j
shows evidence for the previous existence of twin melting
peaks by the fact that the endotherms are wider for Figure 3 Melting endotherms of (a) 70-residues, (b) and (c)
60-residues.--, First melt; . . . . . , second melt. An of un-
fibres at their natural draw ratio than they are for drawn parent fibre: (a) 0.11015;(b) 0.0016;(c) 0.012. Draw ratios
fibres in the undrawn state or at a draw ratio of 10. of parent fibres shown in parentheses, Peak temperatures
Between the undrawn state and the natural draw ratio indicated

:84 POLYMER, 1974, Vol 15, F e b r u a r y

 Morphology of cold-drawn HDPE fibres: W. G. Harland et aL
The resolution is far better at higher draw ratios in the
residues than in the fibres. Such differences of detail
are possibly the result of changes in morphology
occurring during the course of heating fibre samples to
determine their melting endotherms. In this connection
Hosemann et aL 1°, ~ have commented on the suscepti-
bility of the crystals of drawn fibre to thicken and give
rise to a higher melting point practically independent
of the original crystal thickness. In principle such
changes cannot occur in the residues and it is concluded
that the melting endotherms of the residues give a more
realistic picture of the fibre morphology.
The first- and second-melting endotherms of the
60-residues are slightly different. After first melting and
solidification both peak temperatures increase by about
2°C, the area of the LTP increases at the expense of the
HTP, and the degree of crystallinity also falls by up
to 5 ~ as observed by Meinel and Peterlin6. These
changes undoubtedly result from a more effective
fractionation of the molecules during recrystallization
and indicate that, while the two crystalline fractions
produced by the drawing process have different melting
points largely owing to differences of fold length in the
fibres, differences in overall crystallite size also exist.
It would appear that the first-melting endotherms of
the residues give the best indication of the morphological
changes brought about by drawing, but unfortunately,
the relative peak areas cannot be resolved accurately.
A rough visual estimate would suggest that about 30
of the lamellar structure of the 60-fibres has been de-
graded and about 20 ~ in the case of the 60-fibre of
higher initial orientation.
The endotherms of the 70-residues are more difficult
to interpret; a single peak is obtained from the first
melting and a double peak from the second melting.
Identical behaviour has been described by Meinel and
Peterlin 6 for residues derived from drawn HDPE film.
Their explanation, which has already been given in the
introduction, is feasible if, as they claim, tie molecules
and molecules derived from oxidized lamellae are in-
volved in a fractional crystallization process during
solidification following the first melting. Since this
claim cannot be valid for 60-residues, which have
double-peaked endotherms when first melted, and since
there is no reason to suspect any radical difference
between drawing 60, 67-5, and 70-fibres, their explana-
tion is of doubtful validity. While the experimental
data from this investigation offer no explanation for
the phenomenon, it should be noted that geometrical
differences between crystals give rise to different surface
free energy contributions to melting and hence two
crystalline fractions of different thickness may melt
at the same temperature. Such an occurrence would,
however, be fortuitous. Fortunately for present purposes
an explanation is not essential.
The absence of twin melting peaks for 70-fibres
(Figure 2) and for the first melting of 70-residue (Figure
3) makes estimation of the fraction of lamellar structure
degraded during drawing difficult. Judged from a com-
parison of endotherms obtained during the second
melting of 60 and 70-residues there does not appear to
be any significant difference. However, these endotherms
are not a reliable guide and if, as claimed by Meinel
and Peterlin ~, HDPE with a crystalline content of more
than 70 ~ becomes less crystalline at extents of drawing
below the natural draw ratio while polymer of less
than 7 0 ~ crystallinity shows only an increase, it is a
reasonable deduction that the fraction of lamellae
degraded in the 70-fibres is somewhat greater than for
the 60-fibres. Certainly there is no evidence for complete
destruction of lamellar structure in fibres as has been
suggested for drawn HDPE film.
According to Meinel and Peterlin 1 the destruction
of the original lamellar structure is nearly completed
at a draw ratio of about 10, and further deformation
proceeds largely by longitudinal slip of newly formed
microfibrils that are believed to be attached to one
another by a small number of tie molecules which
transverse quasi-amorphous boundary layers. While
this mechanism may be consistent with the negligible
changes which occur between draw ratios of 10 and 15
it does not assist in explaining the disappearance of the
LTP at draw ratios between 15 and 20, which was not
observed in the work of Meinel and Peterlin6 on drawn
films. Another significant difference between the two
investigations is that rupture of the films occurred at
nominal stresses less than the yield stress, whereas
rupture of the fibres occurred at nominal stresses appre-
ciably greater than the yield stress (Table 2). The different
behaviour of the fibres suggests that in their case a
more coherent fibrillar structure is developed and
undergoes further deformation by slipping of constituent
blocks of folded chains until lateral cohesive strength is
improved to the point where it equals that of the fibrils,
or that of interfibrillar tie molecules, and the fibre
ruptures. Such a mechanism would destroy the identity
of the original crystalline blocks used to build the
fibrils, and hence the crystalline phase would exhibit a
single melting point.
The experimental data and deductions also have a
bearing on the investigations of Ward and Williams7
into the distribution of buried chain folds in the lamellar
structure of cold-drawn bulk polyethylene. Using
gel permeation chromatography to elucidate the distribu-
tion of chain lengths in crystalline residues, they detected
multiple peaks corresponding to multiple chain traverses
in lamellae derived from branched polymer, but obtained
a single broad distribution from residues of linear
polyethylene. Since the twin melting peaks discussed
in this paper have been attributed to the creation of
two crystalline fractions of different thickness, it is
interesting to question why they were not detected in
the investigation of Ward and Williams. The reason
is almost certainly because the residues of both fractions
contain buried chain folds and hence have distributions
of chain lengths which when combined overlap to
produce a single-peaked broad distribution. The same
concept also serves to explain the observation of Meinel
and Peterlin6 that annealing residues just below their
melting point removes the LTP and leaves a broad
low-temperature tail in the endotherm; annealing would
eliminate the chain folding and produce an imperfect
chain-extended structure with a broad melting range.
Since the present work contains evidence that the
extent of lamellar degradation incurred by drawing is
less for 60-fibres than 70-fibres, it is probably much
less still or even negligibly small, for cold-drawn branched
polyethylene with a crystalline content of less than 50 ~o
and a much higher compliance. Therefore, the crystalline
residues from cold-drawn low-density polymer and
undrawn HDPE should have a distribution of molecular
weight unconfounded with that of the crystals of a
POLYMER, 1974, Vol 15, February 85
Morphology of cold-drawn HDPE tTbres: 14/. G. Harland et al.
second fraction of significantly different dimensions, as
in fact observed by Ward and WilliamsL
Ward and Williams concluded that the absence of
multiple peaks in the crystalline residues of cold-drawn
HDPE was the result of large fluctuations in crystal
thickness 7. It will be noted that the above explanation
only differs in detail; it has been pursued to make it
abundantly clear that twin peaks in melting endotherms
do not have the same origin as the multiple peaks in the
gel permeation chromatograms.
CONCLUSIONS
The appearance and disappearance of twin peaks in the
melting endotherms of cold-drawn fibres of HDPE and
in the melting endotherms of the corresponding residues
obtained by removal of the amorphous phase by oxida-
tion with nitric acid is consistent with a mechanism of
drawing which involves degradation of a fraction of the
original lamellar structure and the formation of a
microfibrillar crystalline structure. The two crystalline
fractions giving rise to the twin melting peaks are the
86 POLYMER, 1974, Vol 15, February
original lamellae and tom-off blocks of folded chains.
In a fibre of 70 Yo crystallinity and low orientation the
extent of lamellar degradation is not more than about
40Yo and is less for fibres of lower crystallinity and
higher orientation.
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1 Meinel, G. and Peterlin, A. J. Polym. Sci. (A-2) 1971, 9, 67
2 Peterlin, A. in 'Man-Made Fibres' (Eds H. Mark, S. M. Atlas
and C. Cernia), Interscience,New York, 1967, Vol 1, pp 283-340
3 Meinel, G., Morossoff, N. and Peterlin, A. J. Polym. Sci.
(4-2) 1970, 8, 1723
4 Hosemarm, R. J. dppl. Phys. 1963, 34, 25
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(C) 1966, 1, 263
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8 Duch, E. and Kuchler, B. J. Electrochem. Soc. 1956, 60, 218
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1967, 237, 317
ll Hosemann, R. and Wilke, W. Makromol. Chem. 1968, 118,
23O